US3874879A - Article with oxidation protected adhesive and anti-static layer - Google Patents

Article with oxidation protected adhesive and anti-static layer Download PDF

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US3874879A
US3874879A US255487A US25548772A US3874879A US 3874879 A US3874879 A US 3874879A US 255487 A US255487 A US 255487A US 25548772 A US25548772 A US 25548772A US 3874879 A US3874879 A US 3874879A
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oxide
support
subbing layer
layer
photographic
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Arthur A Rasch
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to US255487A priority Critical patent/US3874879A/en
Priority to CA168,437A priority patent/CA1013606A/en
Priority to FR7317446A priority patent/FR2185504B1/fr
Priority to AR248074A priority patent/AR201662A1/es
Priority to IT24298/73A priority patent/IT998112B/it
Priority to DE2325729A priority patent/DE2325729C2/de
Priority to BE131410A priority patent/BE799893A/xx
Priority to GB2441273A priority patent/GB1414528A/en
Priority to JP5709073A priority patent/JPS5710420B2/ja
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/85—Photosensitive materials characterised by the base or auxiliary layers characterised by antistatic additives or coatings
    • G03C1/853—Inorganic compounds, e.g. metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/155—Nonresinous additive to promote interlayer adhesion in element
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/162—Protective or antiabrasion layer

Definitions

  • An article such as photographic article, is disclosed characterized by a dielectric support, a hydrophilic colloid coating and a subbing layer comprised of an electrical conductor, such as a metal, which is oxidiazable if left unprotected and a protective inorganic oxide intimately intermixed with the electrical conductor.
  • the subbing layer can be used to protect against the accumulation of static charge and nonadhesion of the colloid coating to the support.
  • a radiation-sensitive material such as silver halide can be associated with the colloid coating.
  • This invention relates to improving the adhesion of a hydrophilic colloid coating to a dielectric support while protecting the resulting article from static electrical discharge.
  • this invention relates to an article having a hydrophilic colloid coating and a dielectric support which are bonded together by an interposed conductive adhesive layer having a surface resistivity sufficiently low to allow the lateral conduction of electrical charge.
  • this invention relates to a photographic article containing a radiationsensitive material in which a hydrophilic colloid coating is bonded to a dielectric support by an interposed adhesive and anti-static subbing layer.
  • One approach that has been suggested in the art for dissipating or controlling static electrical charges on dielectric photographic supports involves the utilization of a thin metal coating having sufficient conductivity to prevent high, localized static charge accumulation.
  • metallic anti-static coatings are that when they are deposited in thin films of less than about a 100 angstroms they become oxidixed during storage in association with the photographic emulsion coatings, so that their conductances progressively decline and, hence, their antistatic properties deteriorate. If the metal coatings are applied in sufficient thicknesses to offset their declining conductivities in the photographic environment, the increased thicknesses produce undesirable increases in optical density. In either instance the metal anti-static coating can interact with the photosensitive emulsion coating to produce undesirable fogging.
  • the metal coating may inhibit bonding of a photographic emulsion to the support, so that metal antistatic coatings are typically placed on the support surface opposite to that of the photographic emulsion coating.
  • a further disadvantage is that when a support having a freshly deposited metal anti-static layer thereon is wound in reel form, the metal frequently will adhere to both adjacent surfaces. When this occurs the metal may cause blocking i.e., prevent unwinding of the reel or, if unwinding is in fact accomplished, the
  • metal coating may be partially and randomly transferred to the opposite surface of the support.
  • vapor codeposited metal inorganic oxide layers are readily adherent to siliceous surfaces, such as glass, and may be used to impart anti-static properties to glass surfaces, such as windows, lenses, Windshields and the like. It has been recognized that these metal inorganic oxide layers may in turn receive vapor deposited overlayers, such as vapor deposited metal oxide, metal halide and metal overlayers.
  • vapor deposited overlayers such as vapor deposited metal oxide, metal halide and metal overlayers.
  • metal-inorganic oxide layers are compatible with the demanding requirements of photographic use and processing environments.
  • vapor deposited overlayers have been associated with metalinorganic oxide layers, such overlayers differ markedly in physical properties from hydrophilic colloids.
  • l-lydrophilic colloid coatings are neither dimensionally stable nor are they protective in aqueous solutions.
  • hydrophilic colloids ingest water when brought into contact with aqueous solutions, such as photographic processing solutions. The ingestion of water creates substantial dimensional changes and/or large internal stresses in the hydrophilic colloid, particularly at a bonding surface.
  • a hydrophilic colloid coating may ingest a quantity of water several times its original weight leading to doubling, tripling or greater increase in its original thickness.
  • a hydrophilic colloid When a hydrophilic colloid is deposited directly on a support, such as a film support, it can be sloughed from the support on swelling of the layer during exposure to aqueous solutions. Accordingly, the art has heretofore generally utilized subbing layers to facilitate adhesion of hydrophilic colloid coatings to support surfaces.
  • the subbing layer is, of course, brought into direct contact with the processing solutions and must be resistant to attack thereby if the colloid is to remain bonded to the support.
  • an article comprising a dielectric support, a hydrophilic colloid coating and a subbing layer which is contiguous to the support and the hydrophilic colloid coating and is bonded to each.
  • the subbing layer exhibits a surface resistivity of less than l0 ohms per square and is comprised of an electrical conductor capable of oxidation to a less conductive state and a protective inorganic oxide intimately intermixed with the electrical conductor in a'concentration sufficient to retard oxidation of the electrical conductor.
  • a hydrophilic colloid coating can be firmly bonded to a dielectric support surface by means of an adhesive anti-static layer which is contiguous to the supporting surface and to the hydrophilic colloid.
  • the adhesive anti-static layer is a binderless layer which consists essentially of an electrical conductor and a protective inorganic oxide.
  • binderless layer refers to a layer that is substantially free of organic adhesive materials and refers particularly to the absence of those organic adhesive and binder materials commonly utilized in the photographic arts, such as natural and synthetic polymeric binders and colloidal vehicles.
  • the adhesive layer performs the functions both of a conventional anti-static layer and a conventional subbing layer and may be used in combination with either or both, but is preferably substituted for conventional antistatic and subbing layers.
  • the antistatic subbing layers exhibit conductivity characteristics of improved stability when incorporated into articles, particularly photographic articles, to adhesively bond a hydrophilic colloid coating to a support. It is also surprising that the hydrophilic colloid coating remains tenaciously bonded by the subbing layer of this invention to the support surface when the support surface is hydrophobic, when the article is immersed in colloid swelling aqueous solutions and when the article is subjected to mechanical flexure of the support and colloid.
  • photographic articles bearing photosensitive emulsion coatings are often brought into association with alkaline, acid and/or neutral aqueous solutions in accordance with procedures well known to those skilled in the art.
  • the emulsion coating being water permeable, ingests appreciable quantities of aqueous solution, and the increase in volume of the emulsion coating can produce marked dimensional changes and/or internal stresses.
  • the subbing layer utilized in the practice of this invention remains comparatively stable during such photographic processing.
  • the subbing layer is also quite adherent even when subjected to mechanical stress, as. for example, when binding a colloid coating to a flexible support that is wound or repeatedly flexed.
  • the subbing layer exhibits a surface resistivity of less than 10 ohms per square, this being generally recognized as the maximum surface resistivity permissible if charge is to be conducted from a support. In photographic applications it is generally preferred that the layer exhibit a surface resistivity of less than 10 ohms per square. In order to insure that in all localized areas a surface resistivity of less than 10 ohms per square is attained it is preferred that the subbing layer have an overall surface resistivity of less than 10 ohms per square. With anti-static layers having overall surface resistivity of less than ohms per square it has been observed that photographic reproductions can be uniformly and reliably obtained with no evidence of optical alterations attributable to localized discharge of static electrical charge.
  • surface resistivity is determined by measuring the resistance between two parallel electrodes of a given length spaced apart by the same distance along a surface. Since an increase in the length of the electrodes tends to decrease the resistance observed by an amount equal to that by which the resistance would be increased by lengthening the spacing between the electrodes by a like increment, it is apparent that the electrode length and spacing is not material so long as they are identical. hence, the surface resistivity expressed in ohms per square is a resistance measurement taken forthe special case in which electrode length and spacing are identical and therefore mutually canceling parameters.
  • the electrical conductor typically a metal
  • the electrical conductor need not itself be resistant to oxidation in the photographic environment in which it is used. That is, it is noted that metals employed according to this invention in combination with inorganic oxides are protected against excessive oxidation in use even where layers formed entirely by like quantities of the same metals have been observed to be highly oxidized.
  • metals that are noted to be highly useful in the practice of this invention are silver, copper and nickel. Still other metals which are not objection- I ably reactive with the dielectric support, hydrophilic colloid coating and the radiation-sensitivematerials and addenda which are present in photographic applications can'be used, depending upon the specific pa- I rameters, such asinitial cost, optical density, conductance, short and long term oxidation resistance, etc., that may be operative for any particular application.
  • the inorganic oxide component of the subbing layer functions to protect the metal against oxidation.
  • inorganic oxides are dielectric materials, and it is a surprising feature of this invention that they are capable of protecting the metal without increasing the elec: trical resistance of the subbing layer beyond useful anti-static levels.
  • the protective inorganic oxides are characteristically water insoluble and substantially chemically inert toward common photograhpic processing solutions as well as toward photographic emulsion coatings.
  • Preferred metal oxides are those which exhibit a low level of optical density and, most preferably, are substantially transparent. Oxides of silicon,
  • silicon monoxide and silicon dioxide are preferred oxides for the practice of this invention, since they are substantially water insoluble and chemically inert in photographic processing and use environments.
  • Silicon oxides are also preferred, since they can be vapor codeposited with metals by heating to vaporization temperatures that are low as compared to those required for vaporizing other protective oxides.
  • Metal oxides such as aluminum oxide, magnesium oxide, tantalum oxide, boro-silicon oxide (e.g., borosilicate) and titanium oxide are also recognized to be particularly suited to the practice of this invention.
  • the protective oxides are usable in both crystalline and amorphous forms. It is specifically contemplated that glasses may be utilized, particularly glass forming mixtures of oxides. The use of crystalline oxide vapors onto a support.
  • the metal and protective oxide mixture can be blended at a molecular level as taught by Colbert et al, cited above, or can be a mixture of metal particles of up to 200 angstroms in diameter in a continuous matrix of protective oxide as noted, for example, by Milgram and Lu, 39, 4219-24, Journal of Applied Physics. Generally the most intimate physical intermixture obtainable of metal and protective oxide is preferred.
  • the proportions of metal and protective oxide can be varied as required to yield the desired balance of conductance and oxidation resistance properties.
  • the minimum metal content of the subbing layer is determined by its maximum acceptable surface resistivity.
  • Ser. No. 255,331 filed on May 22, 1972, titled AN AR- TICLE HAVING A HYDROPHILIC COLLOID LAYER ADHESIVELY BONDED TO A HYDRO- PHOBIC POLYMER SUPPORT
  • a layer finorganic oxide interposed between a hydrophilic colloid coating and a hydrophobic support surface is capable of improving the colloid coating adherency to the support.
  • chromium and silicon oxides intended to exhibit subbing layer surface resistivities of less than 10 ohms per square and to improve hydrophilic colloid coating adherency chromium concentrations of from 80 to 30 percent by weight and silicon oxide concentrations of from 20 to 70 percent by weight (each percentage being based on the total weight of the subbing layer) are fully satisfactory.
  • the overall thickness of the subbing layer can be widely varied. To the extent that the layer is formed so thin that it exhibits undue surface resistivity-Le, does not fully cover the support surfacethe advantages of this invention may be at least partially diminished. At the same time for many photographic applications it is desirable to limit the layer thickness employed so that the optical density of the photographic article is not objectionably increased. For most photographic applications layer thicknesses of from to 1,000 angstroms are desirable, with thicknesses of from 50 to 500 angstroms being preferred.
  • subbing layers utilized in the practice of this invention may be advantageously applied to those conventional photographic article supports which are dielectric-that is, exhibit a surface resistivity in excess of at least 10 ohms per square and, most commonly, 10 ohms per square-and, particularly to those dielectric supports which present a hydrophobic bonding surface.
  • subbing layer is applied to any support of greater surface resistivity, itwill impart improved protection against the accumulation of static electrical charge.
  • the support is hydrophobic in character
  • the subbing layer presents to the colloid coating which, follows a hydrophilic bonding surface. This then eliminates any further need for resort to additional surface preparations of hydrophobic supports for rendering them hydrophilic and hence more adherent to the hydrophilic colloid coating. It is, of course, recognized that such conventional hydrophilic surface preparations can still be utilized prior or subsequent to depositing the subbing layer of this invention, if this is desired. For example, it may be desirable to coat a hydrophilic colloid coating over the adhesive anti-static subbing layer of this invention to act as a subbing layer for one or more subsequent radiation-sensitive colloid coatings.
  • the subbing layer can be utilized on any conventional dielectric supporting surfaces and is particularly effective in bonding hydrophilic colloid to a hydrophobic dielectric supporting surface.
  • Typical hydrophobic polymers which form supporting surfaces according to this invention include cellulose esters such as cellulose nitrate and cellulose acetate; poly(vinyl acetal) polymers, polycarbonates, polyesters such as polymeric, linear polyesters of bifunctional saturated and unsaturated aliphatic and aromatic dicarboxylic acids condensed with bifunctional polyhydroxy organic compounds such as polyhydroxy alcohols-cg, polyesters of alkylene glycol and/or glycerol with terephthalic, isophthalic, adipic, maleic, fumaric and/or azelaic acid; polyhalohydrocarbons such as polyvinyl chloride; and polymeric hydrocarbons, such as polystyrene and polyolefins, particularly polymers of olefins having from 2 to 20 carbon stoms.
  • the above polymers may be utilized in the form of flexible films or other unitary dielectric supports or may be utilized as coatings on glass, paper and polymer dielectric supports.
  • a preferred class of coated dielectric supports is alpha-olefin resin coated paper supports, such as paper supports coated with polyethylene, polypropylene, ethylene-butene coplymers and the like.
  • the hydrophilic coat-ing to be adhesively bonded to the dielectric support can be formed from one or more hydrophilic, water permeable colloid forming substances including both naturally occurring substances such as, for example, proteins such as gelatin and gelatin derivatives; cellulose derivatives; polysaccharides such as dextran, gum arabic and the like and synthetic polymer substances, such as water soluble polyvinyl compounds like poly( vinylpyrrolidone), acrylamide polymers and the like.
  • the hydrophilic colloids utilized can also contain other synthetic polymeric compounds such as those which increase the dimensional stability of the colloid layers.
  • Suitable synthetic polymers include those described, for example, in Nottorf U.S. Pat. No. 3,142,568, issued July 28, 1964; White U.S. Pat. No. 3,193,386, issued July 6, 1965; Houck et a1. U.S. Pat. No. 3,062,674, issued Nov. 6, 1962; l-louck et a1.
  • the hydrophilic colloid can be hardened by various organic or inorganic hardeners, alone or in combination, such as the aldehydes and blocked aldehydes described in Allen et al. US. Pat. No. 3,232,764, issued Feb. 1, 1966, ketones, carboxylic and carbonic acid derivatives, sulfonate esters, sulfonyl halides and vinyl sulfonyl ethers as described in Burness et al. US. Pat. No. 3,539,644 issued Nov.
  • active halogen compounds epoxy compounds, aziridines, active olefins, isocyanates, carbodiimides, polymeric hardeners such as oxidized polysaccharides like dialdehyde starch and oxyguargum and the like.
  • the article formed is employed in forming an image by exposure to activating radiation that portion of the article to be bonded to the support will contain in or on it a radiation-sensitive material.
  • This material may be panchromatic or orthochromatic material, sensitive only to x-rays or sensitive to selected portions of the electro-magnetic spectrum.
  • the radiation-sensitive portion of the photographic article can contain a single, unitary hydrophilic colloid coating having dispersed therein the radiation sensitive material together with photographic addenda to form a radiation-sensitive emulsion colloid coating (e.g., a photographic or photosensitive emulsion coating) having a hydrophilic surface.
  • the radiation-sensitive portion of the article can comprise a plurality of coatings with the radiation-sensitive material or materials being contained in some or all of the coatings, but not necessarily in the hydrophilic colloid coating immediately adjacent the inorganic oxide subbing layer.
  • a plurality of colloid coatings can be present sensitized within separate segments of the visible spectrum.
  • the hydrophilic colloid coating nearest the support is itself substantially free of radiation-sensitive material as coated. While each of the coatings can comprise a hydrophilic colloid coating, it is recognized that only the bonding surface of the radiation-sensitive portion of the article need be comprised of hydrophilic colloid in order to achieve the objectives of this invention.
  • Suitable hydrophilic colloid coatings which can be bonded to a hydrophobic support surface but which contain no radiation-sensitive material, such as silver halide, when coated include, for example, antihalation layers, nucleated chemical transfer receiving layers, dye-mordant layers and the like.
  • Suitable radiation-sensitive materials which can be employed in practicing this invention are sensitive to electromagnetic radiation and include such diverse materials as silver salts, zinc oxice, photosensitive polycarbonate resins and the like.
  • Silver halides are preferred radiation-sensitive materials and are preferably associated with a colloid or synthetic polymer dispersion vehicle to form an emulsion coating.
  • Silver halide emulsions can comprise, for example, silver chloride, silver bromide, silver bromoidide, silver chlorobromide, silver chloroiodide, silver chlorobromoiodide crystals or mixtures thereof.
  • the emulsions can be coarse or fine grain emulsions and can be prepared by a variety of techniques, e.g.
  • single jet emulsions such as those described in Trivelli and Smith The Photographic Journal, Vol. LXXIX, May, 1939 (pp. 330-338), double jet emulsions such as Lippmann emulsions, ammoniacal emulsions, thiocyanate or thioether ripened emulsions 8 such as those described in Nietz et al. US. Pat. No.. 2,222,264, issued Nov. 19, 1940; Illingsworth US. Pat. No. 3,320,069, issued May 16, 1967, and McBride U.S.
  • the silver halide emulsions employed in the articles of this invention can be sensitized with chemical sensitizers, such as with: reducing compounds; sulfur, selenium or tellurium compounds; gold, platinum or palladium compounds; or combinations of these.
  • chemical sensitizers such as with: reducing compounds; sulfur, selenium or tellurium compounds; gold, platinum or palladium compounds; or combinations of these.
  • the radiation-sensitive colloid coatings can additionally include a variety of conventional addenda both for the colloid and for the radiation-sensitive material.
  • photographic emulsion layers employed according to this invention may include development modifiers, antifoggants and stabilizers, plasticizers and lubricants, brighteners, spectral sensitization agents and color forming materials as set forth in paragraph IV, V, XI, XIV, XV, and XXII, respectively, of Product Licensing Index, Vol. 92, December 1971, publication. 9,232, pages 107-110.
  • photographic articles of this invention can be processed with aqueous photographic processing solutions.
  • Photographic articles containing the inorganic oxide subbing layers described herein can also be used in non-aqueous processinge.g., in so-. called dry processing systems.
  • the subbing layers described herein can be used in silver halide containing articles designed for recording print out im-' ages as described in Fallesen US. Pat. No. 2,369,449 issued Feb. 13, 1945 or Bacon et al. U.S. Pat. 3,447,927 issued June 3, 1969; direct print images as described in Hunt US. Pat. No. 3,033,682 issued May 8, 1962 and McBride US. Pat. No. 3,287,137 issued Nov.
  • anti-static or conducting layers other than I or in addition to adhesive anti-static subbing can incorporate anti-static or conducting layers other than I or in addition to adhesive anti-static subbing.
  • layers of this invention can comprise soluble salts,
  • FIG. 1 illustrates an article 1 comprising a dielectric support 3, such as a hydrophobic polymer support.
  • a hydrophilic colloid coating 5 is located over the support and is adhesively bonded thereto by adhesive antistatic layer 7 according to this invention.
  • FIG. 2 illustrates a photographic article 10 in which a dielectric support 12 is provided with a dielectric hydrophobic polymer layer 14 adjacent one major surface.
  • a radiation-sensitive hydrophilic colloid coating 16 containing radiation-sensitive material is adhesively bonded to the hydrophobic polymer layer by adhesive anti-static subbing layer 18.
  • H6. 3 illustrates a photographic article 100 in which a dielectric support 102 is provided with a dielectric hydrophobic polymer layer 104 adjacent one major surface.
  • An adhesive anti-static subbing layer 106 bonds a radiation-sensitive portion 108 of the article to the hydrophobic polymer surface presented by the layer 104.
  • the radiation-sensitive portion 108 is comprised of a hydrophilic colloid layer 110, which is as coated substantiallyfree of radiation-sensitive materials, and a radiation-sensitive emulsion layer 112, which overlies the layer 110.
  • EXAMPLE 1 In a specific illustration of this invention a subbing layer formed of an intimate intermixture of chromium and silicon monoxide is produced on a polyethylene terephthalate film support which may be utilized without any surface treatment or with a conventional subbing layer formed of a terpolymer of acrylonitrile, vinylidene chloride and acrylic acid. Deposition of the subbing layer is accomplished utilizing a vacuum system in which a length of the film about 5 inches wide With the support in place on the drive rolls and with the chromium and silicon monoxide cermet present as a powder in the crucible the vacuum chamber in which the support and crucible are located is pumped down to 2.3 X 10 Torr. and the cermet is heated by sweeping an electron beam over the surface of the powder. When a sufficiently high temperature is reached for the cermet to sublime readily, the shutter is opened and the support coated to the desired thickness as is determined using a conventional quartz crystal thickness monitor.
  • optical densities are in each instance net optical densities and are determined using an optical densitometer as the difference between the optical densities of otherwise identical coated and uncoated supports.
  • the surface resistivities are determined by placing electrodes on the coated surface of the support in parallel relation and separated by a spacing equal to their length. The surface resistivity can then be read directly in ohms as the resistance separating the electrodes.
  • the chromium and silicon monoxide layers are unaffected when bathed in common photographic processing solutions, such as aqueous alkaline developing solutions and aqueous acid fixing and stop baths.
  • common photographic processing solutions such as aqueous alkaline developing solutions and aqueous acid fixing and stop baths.
  • the low electrical surface resistivity of the coatings provides excellent anti-static protection to the supports.
  • a chromium and silicon monoxide cermet is placed in a crucible a distance of 12 inches below the lower surface of the support for electron beam heating 60 to produce a vapor source.
  • a mask is provided to limit access of the vapor to the support surface, and a shutter is provided in the mask to allow selective areal access of the vapor to the support.
  • the support loop is transported by the drive rolls to allow successive layer thicknesses resulting from varied shutter opening times to be deposited at different locations on the support.
  • Example l Utilizing the same vacuum system as described in Example l a number of layers of intimately intermixed chromium and silicon monoxide are deposited on a terpolymer treated polyethylene terephthtalate support of the type described in Example 1 using as a vapor source a- 1:1 weight ratio of chromium and silicon monoxide. With the source heated in the electron beam to a point where it is subliming at a high rate, the shutter protection for the support is opened and the support is drawn past the shutter opening at rate such that the chromium and silicon monoxide layer condensing on the support forms a layer thickness of approximately 70 angstroms thick.
  • EXAMPLE 4 A number of anti-blocking coatings are made on rolls of polyethylene terephthalate support in the following manner: A roll is loaded into a conventional vacuum roll coater, and an anti-blocking glass to be deposited, such as a borosilicate glass, e.g., Code 8,329 glass (manufactured by Jena Glaswerk Schott and Gen.,
  • the anti-blocking glass is, of
  • anti-blocking coatings are deposited anti-static layers by the. same procedures.
  • a layer formed of intermixed chromium and silicon monoxide is deposited using a l:1 weight ratio of chromium and silicon monoxide cermet.
  • layers of nickel and aluminum are also deposited.
  • the thicknesses and opti cal densities of the supports with the metal and intermixed metal and methal oxide layers is set forth below in Table IV.
  • the coatings are stored in rolls for 2 weeks under ambient conditions and then overcoated on a conventional emulsion coating machine with a silver bromoiodide photographic emulsion at a coverage of 400 mg. of silver/ft?
  • a conventional emulsion coating machine with a silver bromoiodide photographic emulsion at a coverage of 400 mg. of silver/ft?
  • supports of untreated polyethylw ene terephthalate and polyethylene terephthalate coated with a conventional subbing layer for emulsion adhesion comprised of a terpolymer of methyl acrylate, vinylidene chloride and acrylic acid are also overcoated with the photographic emulsion.
  • EXAMPLE 5 In order to further compare the adherency of the emulsion coatings to the supports several photographic articles are prepared as described above in Example 4 and, additionally, an article is similarly prepared incorporating a borosilicate glass layer as described above in Example 4 between the emulsion coating and support.
  • the emulsion coating is scribed to the support with an 0.1 mm. stylus and the article is processed under conditions of high agitation. The amount of peeling from the scribed mark is taken as a relative measure of adhesion.
  • a 1-inch circle of the emulsion coating is submitted to a wash cycle at 71C. and dried. Thereafter the percent peel from the sample is measured.
  • the layer compositions are compared and their performance set forth in Table V.
  • the aluminum 'layer is totally ineffective to bond the emulsion coating to the support under the oxidizing conditions presented and it is not to be expected that other oxidizable metal layers would behave in a significantly different manner.
  • the glass layer while adhering less well than the conventional terpolymer subbing layer, is nevertheless significantly better than the metal layer and is capable of providing acceptable adhesion of the emulsion coating to the support.
  • the intermixed metal and metal oxide layer provides a very stable adhesion of the emulsion coating to the support which, in terms of mm. of peel, is superior to the adherency provided by the conventional terpolymer subbing layer.
  • chromium When other metals of an oxidizable nature, such as silver, nickel, and copper, are substituted for chromium similarly improved adherency and anti-static characteristics are achieved, although the most invariant surface resistivities are achieved using chromium.
  • Other vapor depositable metal oxides such as silica, alumina, magnesia, titania and tantalum oxide, are also capable of protecting the intermixed metals against oxidation with the same degree of effectiveness as silicon monoxide, although the silicon oxides are preferred because of their lower vapor deposition temperatures. With vapor codeposited interrnixtures of the above enumerated metals and metal oxides high levels of adherency, oxidation resistance, anti-static properties are obtained together with low surface resistivities for given levels of optical density.
  • a photographic article comprising a radiation sensitive material, a dielectric hydrophobic polymer support, a hydrophilic colloid coating and an adhesive hydrophilic subbing layer which is contiguous to said support and said hydrophilic colloid coating and is bonded to each, the improvement in which said adhesive subbing layer is additionally an anti-static layer exhibiting a surface resistivity of less than 10 ohms per square and is binderless and consists essentially of an intimate blend of a. a metal electrical conductor capable of oxidation to a less conductive state and at least about 20 weight, based on the weight of said blend of b. a protective inorganic oxide selected from the group consisting of silicon oxide, magnesium oxide, aluminum oxide, tantalum oxide, titanium oxide, boro-silicon oxide and mixtures thereof; the thickness of said adhesive subbing layer being from about 50 to about 500 angstroms.
  • a photograpic article comprising a radiationsensitive material, a dielectric hydrophobic polymer support, a hydrophilic gelatin coating and an adhesive hydrophilic subbing layer which is contiguous to said support and said hydrophilic gelatin coating and is bonded to each
  • said adhesive subbing layer is additionally an anti-static layer exhibiting a surface resistivity of less than 10 ohms per square and is binderless and consists essentially of an intimate blend of a.
  • a metal electrical conductor capable of oxidation to a less conductive state, and at least about 20 weight, based on the weight of said blend of b.
  • a protective inorganic oxide selected from the group consisting of silicon oxide, magnesium oxide, aluminum oxide, tantalum oxide, titanium oxide, boro-silicon oxide and mixtures thereof; the thickness of said anti-static layer being from about 50 to about 500 angstroms.
  • said protective inorganic oxide consisting essentially of silicon monoxide.
  • said subbing layer consisting essentially of a mixture of chromium and silicon oxide.
  • said radiation-sensitive material being a silver halide.
  • said support being polyethylene terephthalate
  • said radiation-sensitive material being a silver halide
  • said subbing layer consisting essentially of silicon oxide and chromium.
  • said silver halide being silver bromochloride.
  • a photographic article comprising a dielectric hydrophobic polymer support, a first hydrophilic gelatin coating, a second hydrophilic gelatin coating bonded to said first hydrophilic gelatin coating and containing a radiation-sensitive silver halide, and an adhesive hydrophilic subbing layer which is contiguous to said support and said first hydrophilic gelatin coating and is bonded to each, the improvement in which said adhesive subbing layer is additionally an anti-static layer exhibiting a surface resistivity of less than 10 ohms per square, is substantially transparent and consists essentially of an intimate blend of a. a vapor deposited electrically conductive metal capable of oxidation to a less conductive state and thickness of said anti-static layer being from about 50 to about 500 angstroms. 10. In a photographic article according to claim 9,
  • said electrically conductive metal consisting essentially of chromium.
  • subbing layer consisting essentially of a mixture of chromium and silicon monoxide.
  • said subbing layer consisting essentially of from 80 to 30 percent by weight chromium and from 20 to per- 9 cent by weight an oxide of silicon monoxide.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
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  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US255487A 1972-05-22 1972-05-22 Article with oxidation protected adhesive and anti-static layer Expired - Lifetime US3874879A (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
US255487A US3874879A (en) 1972-05-22 1972-05-22 Article with oxidation protected adhesive and anti-static layer
CA168,437A CA1013606A (en) 1972-05-22 1973-04-11 Article with oxidation protected adhesive and anti-static layer
FR7317446A FR2185504B1 (en(2012)) 1972-05-22 1973-05-15
AR248074A AR201662A1 (es) 1972-05-22 1973-05-17 Elemento fotografico que tiene una capa sustrato adhesiva y antiestatica para unir un revestimiento de coloide hidrofilo a un soporte dielectrico
IT24298/73A IT998112B (it) 1972-05-22 1973-05-18 Elemento fotografico avente un supporto dielettrico rivestito con uno strato antistatico protetto contro l ossidazione
DE2325729A DE2325729C2 (de) 1972-05-22 1973-05-21 Strahlungsempfindliches photographisches Aufzeichnungsmaterial mit einer antistatisch wirksamen Haftschicht
BE131410A BE799893A (fr) 1972-05-22 1973-05-22 Nouveau produit, notamment photographique comprenant une couche intermediaire antistatique
GB2441273A GB1414528A (en) 1972-05-22 1973-05-22 Photographic material
JP5709073A JPS5710420B2 (en(2012)) 1972-05-22 1973-05-22

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US255487A US3874879A (en) 1972-05-22 1972-05-22 Article with oxidation protected adhesive and anti-static layer

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US3874879A true US3874879A (en) 1975-04-01

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US (1) US3874879A (en(2012))
JP (1) JPS5710420B2 (en(2012))
AR (1) AR201662A1 (en(2012))
BE (1) BE799893A (en(2012))
CA (1) CA1013606A (en(2012))
DE (1) DE2325729C2 (en(2012))
FR (1) FR2185504B1 (en(2012))
GB (1) GB1414528A (en(2012))
IT (1) IT998112B (en(2012))

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3961962A (en) * 1973-11-29 1976-06-08 Fuji Photo Film Co., Ltd. Photomask material and method for producing same
US4078935A (en) * 1974-04-30 1978-03-14 Fuji Photo Film Co., Ltd. Support member
US4242438A (en) * 1974-09-06 1980-12-30 Fuji Photo Film Co., Ltd. Photomask material
US4394441A (en) * 1981-01-14 1983-07-19 Fuji Photo Film Co., Ltd. Photographic sensitive materials
US4418141A (en) * 1980-12-23 1983-11-29 Fuji Photo Film Co., Ltd. Photographic light-sensitive materials
US4495276A (en) * 1980-04-11 1985-01-22 Fuji Photo Film Co., Ltd. Photosensitive materials having improved antistatic property
US5213887A (en) * 1991-09-03 1993-05-25 Minnesota Mining And Manufacturing Company Antistatic coatings
US5254448A (en) * 1991-01-08 1993-10-19 Konica Corporation Light-sensitive silver halide photographic material
US5348799A (en) * 1991-09-03 1994-09-20 Minnesota Mining And Manufacturing Company Antistatic coatings comprising chitosan acid salt and metal oxide particles
US5395677A (en) * 1992-06-29 1995-03-07 Fuji Xerox Co., Ltd. Transparent electrophotographic film
US5496690A (en) * 1993-10-29 1996-03-05 Toyo Ink Manufacturing Co., Ltd. Base film having dimensional stability and high transparency, and photographic light-sensitive material comprising same
US6030708A (en) * 1996-10-28 2000-02-29 Nissha Printing Co., Ltd. Transparent shielding material for electromagnetic interference

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS588498B2 (ja) * 1974-06-13 1983-02-16 富士写真フイルム株式会社 写真記録用材料
US4329409A (en) * 1980-08-04 1982-05-11 Hughes Aircraft Company Process for fabricating stable holograms
US4330604A (en) * 1980-08-04 1982-05-18 Hughes Aircraft Company Fabrication of holograms on plastic substrates
JPH063533B2 (ja) * 1983-05-02 1994-01-12 コニカ株式会社 写真感光材料の中間品の製造方法
JPS6362864A (ja) * 1986-09-02 1988-03-19 Seikosha Co Ltd 黒銀色を呈する物品

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2687373A (en) * 1947-08-22 1954-08-24 Cris Trust Process for the production of a metal offset printing plate
US2786778A (en) * 1954-02-05 1957-03-26 Minnesota Mining & Mfg Ink-receptive resinous films
US2808351A (en) * 1952-10-31 1957-10-01 Libbey Owens Ford Glass Co Electrically conducting coated glass or ceramic articles suitable for use as a lens, a window or a windshield, or the like
US2852415A (en) * 1952-10-29 1958-09-16 Libbey Owens Ford Glass Co Electrically conducting coated glass or ceramic articles suitable for use as a lens, a window or a windshield, or the like
US2939787A (en) * 1957-03-01 1960-06-07 Rca Corp Exposure of photochemical compositions
US3181461A (en) * 1963-05-23 1965-05-04 Howard A Fromson Photographic plate
US3356529A (en) * 1964-07-31 1967-12-05 Gen Electric Method for the deposition of an electro-conductive transparent indium oxide coating

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2118059A (en) * 1935-09-20 1938-05-24 Eastman Kodak Co Antistatic photographic film
US3074816A (en) * 1960-10-28 1963-01-22 Westinghouse Electric Corp Light-transmitting, electrically conducting element
DE1422949A1 (de) * 1961-07-18 1968-11-21 Siemens Ag Antistatischer Rollfilm,insbesondere fuer Aufnahmen im Elektronenmikroskop
DE1572266A1 (de) * 1967-04-24 1970-02-19 Fotochem Werke Berlin Veb Verfahren zur Vorbehandlung von Polyesterfilmunterlage fuer den Auftrag von fotografischen Emulsionen
DE1815944C3 (de) * 1968-12-20 1979-11-22 Agfa-Gevaert Ag, 5090 Leverkusen Antistatisches photographisches Material

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2687373A (en) * 1947-08-22 1954-08-24 Cris Trust Process for the production of a metal offset printing plate
US2852415A (en) * 1952-10-29 1958-09-16 Libbey Owens Ford Glass Co Electrically conducting coated glass or ceramic articles suitable for use as a lens, a window or a windshield, or the like
US2808351A (en) * 1952-10-31 1957-10-01 Libbey Owens Ford Glass Co Electrically conducting coated glass or ceramic articles suitable for use as a lens, a window or a windshield, or the like
US2786778A (en) * 1954-02-05 1957-03-26 Minnesota Mining & Mfg Ink-receptive resinous films
US2939787A (en) * 1957-03-01 1960-06-07 Rca Corp Exposure of photochemical compositions
US3181461A (en) * 1963-05-23 1965-05-04 Howard A Fromson Photographic plate
US3356529A (en) * 1964-07-31 1967-12-05 Gen Electric Method for the deposition of an electro-conductive transparent indium oxide coating

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3961962A (en) * 1973-11-29 1976-06-08 Fuji Photo Film Co., Ltd. Photomask material and method for producing same
US4078935A (en) * 1974-04-30 1978-03-14 Fuji Photo Film Co., Ltd. Support member
US4242438A (en) * 1974-09-06 1980-12-30 Fuji Photo Film Co., Ltd. Photomask material
US4495276A (en) * 1980-04-11 1985-01-22 Fuji Photo Film Co., Ltd. Photosensitive materials having improved antistatic property
US4418141A (en) * 1980-12-23 1983-11-29 Fuji Photo Film Co., Ltd. Photographic light-sensitive materials
US4394441A (en) * 1981-01-14 1983-07-19 Fuji Photo Film Co., Ltd. Photographic sensitive materials
US5254448A (en) * 1991-01-08 1993-10-19 Konica Corporation Light-sensitive silver halide photographic material
US5213887A (en) * 1991-09-03 1993-05-25 Minnesota Mining And Manufacturing Company Antistatic coatings
US5348799A (en) * 1991-09-03 1994-09-20 Minnesota Mining And Manufacturing Company Antistatic coatings comprising chitosan acid salt and metal oxide particles
US5457015A (en) * 1991-09-03 1995-10-10 Minnesota Mining And Manufacturing Company Silver halide coated organic polymeric films utilizing chitosan acid salt antistatic protection layers
US5395677A (en) * 1992-06-29 1995-03-07 Fuji Xerox Co., Ltd. Transparent electrophotographic film
US5496690A (en) * 1993-10-29 1996-03-05 Toyo Ink Manufacturing Co., Ltd. Base film having dimensional stability and high transparency, and photographic light-sensitive material comprising same
US6030708A (en) * 1996-10-28 2000-02-29 Nissha Printing Co., Ltd. Transparent shielding material for electromagnetic interference

Also Published As

Publication number Publication date
FR2185504B1 (en(2012)) 1977-11-18
FR2185504A1 (en(2012)) 1974-01-04
JPS4951930A (en(2012)) 1974-05-20
GB1414528A (en) 1975-11-19
JPS5710420B2 (en(2012)) 1982-02-26
DE2325729C2 (de) 1982-12-02
IT998112B (it) 1976-01-20
AR201662A1 (es) 1975-04-08
BE799893A (fr) 1973-11-22
CA1013606A (en) 1977-07-12
DE2325729A1 (de) 1973-11-29

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